EP1296903B1 - Binder for mineral wool products - Google Patents

Binder for mineral wool products Download PDF

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Publication number
EP1296903B1
EP1296903B1 EP01960457.8A EP01960457A EP1296903B1 EP 1296903 B1 EP1296903 B1 EP 1296903B1 EP 01960457 A EP01960457 A EP 01960457A EP 1296903 B1 EP1296903 B1 EP 1296903B1
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EP
European Patent Office
Prior art keywords
anhydride
preferably
process according
acid
added
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EP01960457.8A
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German (de)
French (fr)
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EP1296903A1 (en
Inventor
Thor Husemoen
Erling Lennart Hansen
Povl Nissen
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Rockwood International AS
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Rockwood International AS
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Priority to EP00202335 priority Critical
Priority to EP00202335A priority patent/EP1170265A1/en
Application filed by Rockwood International AS filed Critical Rockwood International AS
Priority to PCT/EP2001/007628 priority patent/WO2002006178A1/en
Priority to EP01960457.8A priority patent/EP1296903B1/en
Publication of EP1296903A1 publication Critical patent/EP1296903A1/en
Application granted granted Critical
Publication of EP1296903B1 publication Critical patent/EP1296903B1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/25Non-macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • C03C25/32Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/328Polyamides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04Preparatory processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28Preparatory processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44Polyester-amides

Description

  • The invention relates to a process for providing a binder for mineral fibers, i.e. man made vitreous fibers, for example glass, slag or stone wool, a binder obtainable via such a process, and a mineral wool product comprising such a binder.
  • Mineral wool products generally comprise mineral fibers bonded together by a cured thermoset polymeric material. One or more streams of molten glass, slag or stone wool are drawn into fibers and blown into a forming chamber where they are deposited as a web on to a travelling conveyer. The fibers, while airborne in the forming chamber and while still hot are sprayed with a binder. The coated fibrous web is then transported from the chamber to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral wool fibers together.
  • During the curing step when hot air is blown through the mat to cure the binder, a binder as disclosed in WO 99/36368 can be displaced within the mineral wool fibers, whereby a non-uniform distribution of the binder results, specifically wherein less binder is to be found at the bottom of the mineral fiber blocks (i.e. the side of the block where the hot air is blown into the product) than in the top thereof.
  • Also during curing, a large amount of the resin may be lost leading to undesirably high emissions and a high binder loss.
  • An object of the present invention is to improve on this situation.
  • US-A-4074988 relates to individual glass fibers which are coated with a composition which includes the condensation product of a polycarboxylic acid or anhydride and a polyfunctional amine.
  • US-A-3341573 describes hydraulic fluid compositions comprising polyamide esters prepared from polyglycol amines and dicarboxylic organic acids.
  • EP-A-0826710 relates to a formaldehyde-free curable aqueous composition comprising a polyacid, an active hydrogen compound containing at least two active hydrogen groups which may be amino groups and a fluoroborate accelerator.
  • EP-A-0354361 is concerned with high molecular weight polyimides formed by polycondensation of particular amino compounds and particular dianhydride compounds.
  • According to a first aspect there is provided a process for providing a binder for mineral fibers, comprising the steps of mixing together under reactive conditions an anhydride and an amine selected from N-substituted ß-hydroxyalkyl amines, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol and tris(hydroxymethyl)amino-methane, whereby water is added thereto once substantially all the anhydride is dissolved in and/or has reacted with the amine. The reaction is thus terminated.
  • A second anhydride is preferably added to the reaction mixture whereby the water is preferably added to the reaction mixture immediately before or together with the second anhydride, or when substantially all of the second anhydride is dissolved in and/or reacted with the mixture of the first anhydride and the amine.
  • Water is most preferably added to the reaction mixture in an amount to make this easily pumpable.
  • Low viscous resin binders for mineral wool are known, wherein the usual procedure is to mix diethanolamine with water before adding any anhydride to minimize viscosity/stirring problems and to obtain the desired water solubility. These resins however contain a high amount of rest monomers, i.e. unreacted starting material, and have the disadvantages of providing a low molecular weight binder which has a long curing time. In order to overcome these extensive curing times, it is often necessary to use a high curing temperature with the accompanying problem that the high curing temperature and long curing time cause extensive evaporation of the binder and non-uniform binder distribution.
  • A binder so obtained, yields a high binder loss, high emission and curing problems.
  • By utilizing a process according to the present invention, a binder is provided for bonding mineral wool products, wherein the amount of rest monomers, i.e. unreacted start material is reduced, and having a higher average molecular weight, whilst still maintaining water solubility.
  • Furthermore, the inventors have shown that utilizing the process according to the present invention, the amount of emissions can be reduced, the binder yield can be raised, the curing time can be shortened, whilst the product quality can be improved.
  • It is theorized that the monomers also take part in the binder cross-linking reaction during curing, but if this amount is too high and the curing time is too long, most of the monomers evaporate.
  • The inventors have shown that providing the binder without water addition from the start of the reaction, reduces the amount of unreacted monomers and increases the curing speed yielding a binder having a higher average molecular weight.
  • Furthermore, the inventors have shown that the binder loss during curing is less because of the presence of less unreacted monomers, whereby a rapid viscosity increase is provided due to the shorter curing time and the higher initial Mw. This rapid viscosity increase makes it difficult for the monomers to evaporate from the reaction mixture instead having time to react as a binder component and take part in the cross-linking reaction. Furthermore, due to the increased viscosity of the binder obtainable by the process of the present invention, there is less displacement of the binder in the mineral wool, when the binder has been applied to the mineral wool and curing is taking place.
  • In an embodiment, the amine is heated firstly to a temperature of at least 40, preferably at least 50 and most preferably to about 60°C whereafter the first anhydride is added, and the reaction temperature then is raised to at least 70, preferably at least about 80 and most preferably to at least about 95°C at which temperature the second anhydride can be added to the reaction mixture when substantially all the first anhydride has dissolved and/or reacted.
  • Alternatively increasing the reaction temperature from 90-95°C to 100-200°C gives a higher conversion of monomers to oligomers.
  • A preferred temperature range is 120-170°C, and most preferred is 130-150°C.
  • The temperature is at least 100°, often at least 120°, and preferably about 130°C. It is normally below 200°, and preferably below 170°, more preferably below about 150°C.
  • The average molecular weight of oligomers is increased when the reaction temperature is raised.
  • The evaporation loss of binder made of resin reacted at higher temperature is lower when cured.
  • A binder produced under these circumstances wherein water is added when the first anhydride has reacted, together with the second anhydride or at the end of the reaction, in an amount to make the binder easily pumpable, enables a binder with an increased average molecular weight to be provided but still having a desired pumpability, viscosity, and water dilutability.
  • A resin according to the present invention but made with water addition from the start has more than 50% unreacted monomers of diethanolamine and polycarboxylic acids (anhydrides reacted with water), less than 15% amide of complete amide formation and an average molecular weight of about 400 and a maximum of about 600.
  • A resin made according to the process of the present invention with water addition at the end, together with a second anhydride, or just before the second anhydride has been added, has less unreacted monomers, especially the polycarboxylic acids, less than 30% compared with water addition from the start, a higher amount of amides, 15% or more of complete amide formation, and an average molecular weight of 500-900 and a maximum of about 2000.
  • The first and second anhydrides, and the amine are also described in claims 1 and 8-12.
  • The reaction mixture used as a binder can also comprise an accelerator, a resin additive, a corrosion inhibitor to curb the effect on pipes and the like, and/or a cross-linking agent as described in claims 13-17.
  • Further characteristics of the process are to be found in claims 18-26.
  • The inventors have shown that the aged strength of the binder mixture can be improved by the addition of silane.
  • The amount of silane in the resin reaction mixture is at least 0.1 %, often at least 0.2% and preferably at least about 1%. It is normally below 5% and preferably below 3% and is often about 1.5%.
  • In order to improve the water solubility of the binder a base might be added upto a pH of about 8, whereby a pH of between about 6-8 is preferred, more preferred being a pH of about 7. The base can be mixed with a polyacrylic acid and added to the resin after the resin reaction is stopped by water addition. The base thus need first be added after the resin is prepared. The base may be mixed with a carboxylic acid group containing polymer before addition. Suitable bases could be NH3, DEA, TEA, or alkali hydroxides.
  • It is found that addition of one or more cross-linking agents with a carboxylic acid group containing polymer increases the curing speed of the binder.
  • The first and second anhydrides are chosen to provide reaction products with a large number of unreacted polycarboxylic acid groups, which is preferable for water solubility. A most preferred binder consists of 30% polymer of DEA (diethanolamine), THPA (tetrahydrophthalic anhydride) and TMA (trimellitic anhydride), 15% DEA monomer, 10% THPA monomer reacted with water to diacid, 5% TMA monomer reacted with water to triacid and 40% water. In the polymer preferably about 50% of the reacted DEA has reacted to an amide and the other 50% of the reacted DEA has reacted to an ester.
  • Another preferred binder consists of about 40% or more polymer, (DEA, THPA, TMA), about 10% or less DEA monomer, about 10% or less THPA monomer and TMA monomer reacted with water to diacid, triacid respectively and 40% water.
  • The invention will now be further clarified by way of the following examples and reference to table 1, wherein a plurality of resin formulations is shown.
  • Resin formulations were made (see tables 1, 2 and 3) .
  • Key to abbreviations in tables:
    • DEA - diethanolamine
    • GLA - glutaric anhydride
    • SCA - succinic anhydride
    • TMA - trimellitic anhydride
    • ADP - adipic acid
    • THPA - tetrahydrophthalic anhydride
    • Base - ammonia, amines or inorganic hydroxides
    • PAA - polyacrylic acid
    • Silan - amino silanes as par example gammaaminopropyltriethoxysilane (prehydrolysed VS 142 from Witco or not hydrolysed A 1100 from Witco or similar from other producers)
    • PTA - phthalic anhydride
    Table 1 Formulation Mol ratio Water add. Rest acid % Rest amine % Rest DEA % Calculated amide % Calculated ester % 1* DEA:THPA 1:1.4 from start 52 91 46 9 45 2* DEA:THPA 1:1.4 during reaction 21 70 24 30 46 3 DEA:THPA 1:1.4 at the end 18 78 23 22 54 4* DEA:THPA:TMA 1:1:0.4 from start 73 90 66 10 24 5* DEA:THPA:TMA 1:0.8:0.6 from start 70 91 64 9 27 6 DEA:THPA:TMA 1:0.9:0.3 before TMA 31 82 50 18 32 7 DEA:THPA:TMA 1:0.8:0.3 before TMA 36 82 47 18 35 8 DEA:THPA:TMA 1:0.6:0.3 before TMA 26 85 63 15 23 9 DEA:THPA:TMA 1:0.6:0.3 with TMA 40 75 55 25 20 10* DEA:THPA:PTA 1:0.8:0.3 from start 77 86 68 14 18 11* DEA:THPA:PTA 1:0.6:0.8 from start 80 87 68 13 19 12 DEA:THPA:PTA 1:0.7:0.3 at the end 17 68 43 32 26 13 DEA:THPA:PTA 1:0.7:0.3 at the end 28 64 42 36 25 14 DEA:GLA 1:1.4 at the end 38 33 12 67 21 15 DEA:SCA 1:1.4 at the end 0 29 19 71 10 16 DEA:THPA:SCA 1:0.6:0.7 at the end 16 54 32 46 22 % Rest acid and % rest DEA are % rest monomers of added monomers. % Rest amine is amine not reacted to amide % Calculated amide is difference between total amin and % rest amine. % Calculated ester is % DEA bound as ester * not according to the invention
    Table 2 Formulation Amine Anhydride Accelerator/ crosslinkers Base Silane (%) Temp. [°C] Mole ratio Water added Rest acid Rest DEA Cal. amide % Cal. ester % 17 DEA THPA + TMA phosphinic acid NH4OH 0.4 130 1.0:0.6:0.3 at the end 18 39 - - 18 DEA THPA + TMA H3PO4 NH4OH 0.4 130 1.0:0.6:0.3 at the end 18 39 - - 19 DEA THPA + TMA phosphinic acid + PAA NH4OH 0.4 130 1.0:0.6:0.3 at the end 18 39 - - 20 DEA THPA + TMA PAA NH4OH 0.4 130 1.0:0.6:0.3 at the end 18 39 - - 21 DEA THPA + TMA phosphinic acid NH4OH 0.4 170 1:0.6:0.3 at the end 10 23 Formulation Average Mw Amount added accelerator / crosslinker in dry matter Curing time, 250 °C [sec.] Delaminating strength [kPa] Remaining strength after ageing [kPa] Binder yield [%] Binder distribution [%] 17 600 3% 60 15.2 9.1 85 Top-bottom is OK 18 600 3% 68 85 Top-bottom is OK 19 600 3% + 10% 25 83 Top-bottom is OK 20 600 10% 28 11.2 4.5 84 Top-bottom is OK 21 not measured 3%
    Figure imgb0001
  • Formulation 22 and 23 were prepared as follows:
  • Formulation 22 Resin:
  • 116 kg DEA was transferred to a 400 l reactor and heated to 60°C whilst stirring.
  • 16.3 kg ADP was added, and the mixture heated and reacted at 130°C for 60 minutes.
  • Thereafter cooled to 85°C and 33.8 kg of THPA was added. Thereafter 82.5 kg PTA was added and the temperature raised to 130°C for 120 minutes.
  • Subsequently the reaction mixture was cooled to 110°C and 100 kg water added.
  • The temperature stabilised at approx. 50°C. The mixture was stirred for a further 15 minutes until homogenous.
  • The resin was cooled and transferred to a storage tank.
  • The resin solids content was determined as 62.2% at 200°C. Rest monomers: 39% of added DEA, 12% of added THPA, 25% of added PTA. Average molweight about 600.
  • The amount of rest monomers was determined by taking seperate samples of the resin for each component. The samples were heated to 200° c in order to remove all water, and then measured.
  • Before use 4% DEA and 25% solids Acumer 1510 calculated on resin solids, 0.4% of sum solids silane and water to 25% solids content, was added.
  • Results of trial
    • Binder yield 60%
    • Delamination strength (EN 1607) 13.4 kPa (Terrænbatts Industri) - Aged 3.6 kPa (70°C/95%RH)
    • Tensile strength 5.5 kPa (Flexi A Batts)
    Formulation 23 Resin
  • 24 kg DEA was transferred to a 80 l reactor and heated to 60°C and stirred.
  • 6.7 kg ADP was added and the mixture heated and reacted at 130°C for 60 minutes.
  • Thereafter cooled to 85°C and 6.9 kg of THPA was added. Thereafter 16.9 kg PTA was added and the temperature raised to 130°C for 120 minutes.
  • Subsequently the reaction mixture was cooled to 110°C and 20.5 kg water added. The temperature stabilised at approx. 50°C.
  • The mixture was stirred for further 15 minutes until homogenous.
  • The resin was cooled and transferred to a storage tank.
  • The resin solids content of 63.4% was determined at 200°C. Rest monomers: 37% of added DEA, 14% of added THPA, 25% of added PTA. Average molweight about 600.
  • The amount of rest monomers was determined by taking out seperate samples of the resin for determination of each component. The samples were heated to 200°C in order to remove all water, and then measured.
  • Before use 4% DEA and 25% solids Acumer 1510 calculated on resin solids, 0.4% of sum solids silane and water to 25% solids content, was added and analysed.
  • Results of trial
    • Binder yield 70%
    • Delamination strength (EN 1607) 12.1 kPa (Terrænbatts Industri) - Aged 4.3 kPa (70°C/95%RH)
  • A number of these formulations were investigated for molecular weight and curing time at 250°C, the results being as follows:
  • Molecular weight analysis of the polymeric part or moiety Formulation:
    • 1) DEA:THPA - water added from start - average Mw 400 - maximum 600
    • 3) DEA:THPA - water added at the end - average Mw 850 - maximum 2000
    • 4) DEA:THPA:TMA - water added from start - average Mw 400 - maximum 600
    • 5) DEA:THPA:TMA - water added from the start - average Mw 500 - maximum 1500
    • 9) DEA:THPA:TMA - water added with TMA - average Mw 500 - maximum 1500
      20.3 kg DEA is heated to 60°C, whereafter 17.7 kg THPA is added during stirring. The temperature is raised to 95°C and reaction continued for 1 hour, whereafter 25.8 kg water and 11.2 kg TMA are added and right after 11.2 kg TMA is added. Temperature is held at 95°C for ½ hour before the reaction is stopped by cooling to room temperature.
      Composition of resin:
      • 15% DEA monomer
      • 10% THPA monomer reacted to acid
      • 5% TMA monomer reacted to acid
      • 40% Water
      • Rest 30% is polymer of DEA:THPA:TMA
    • 16) DEA:THPA:SCA - water at the end - average Mw 550 - maximum 1100
    Curing time at 250 °C
    • DEA:THPA:TMA or PTA - curing time about 2 minutes, formulation 9) and 12), table 1;
    • DEA:THPA:SCA - curing time about 1 minute, formulation 16), table 1;
    • DEA:THPA:TMA or PTA added 20% polyacrylic acid - curing time 25-40 seconds, formulation 9) and 12), table 1;
    • DEA:THPA:SCA added 20% polyacrylic acid - curing time 20 seconds, formulation 16), table 1.
  • The curing time was measured by preheating a droplet of binder placed on a thin glass plate during 45 minutes at 90°C after which it was heated to 250 °C by placing the glass plate on a heating plate and stirred with a thin needle. The time until the binder droplet was cured was measured after placing on said heating plate. The test method was repeated. Two more droplets of the same binder were tested using the same method.
  • Factory trials utilizing the binder according to the present invention on a mineral wool Marine Slab 100 was carried out as follows.
  • Binder formulations were made based on selected resins to which 20% w/w polyacrylic acid was added as a cross-linking agent and 0.2% w/w silane as a coupling agent was added. Curing was carried out at 250°C.
  • The delaminating strength was measured according to EN 1607, whereby ageing is defined as remaining delaminating strength after treatment 15 minutes in an autoclave with 120°C (1 ato).
  • Results
    • Formulation 16, DEA:THPA:SCA - water at the end.
    • Delamination strength 9 kPa - remaining strength after
    • ageing 25% - binder yield 75%
    • Binder distribution top - bottom is OK
    • Formulation 9, DEA:THPA:TMA - water added during TMA addition.
    • Delaminating strength 10 kPa - remaining strength after
    • ageing 68% - binder yield 80%
    • Binder distribution top - bottom is OK
    • Formulation 13, DEA:THPA:PTA - water at the end.
    • Delaminating strength 10 kPa - remaining strength after
    • ageing 52% - binder yield 65%
    • Less binder in bottom than top
    • Reference formulation 1 DEA:THPA - water added from start.
    • Delamination strength 7 kPa - remaining strength after ageing 40% - binder yield < 50%
    • Almost no binder in the 1/3 bottom part which is cut away before delamination measurements.
    Example: Reaction temperature at 130°C compared with 95°C (see Table 2) Formulation 9) reaction temperature 95°C.
    • Molratio DEA:THPA:TMA = 1 : 0.6 : 0.3, coupling agent 0.4% VS 142 of binder solids.
    • Rest monomers: 55% of added DEA, rest monomers 40% of added anhydrides.
    • Average molecular weight of oligomers 500.
    • Evaporation loss of binder solids in factory trial 25-30%
    Product quality:
    • Delamination strength (EN 1607) 10 kPa,
      remaining strength after ageing 6.8 kPa Product quality when using phosphonic acid as curing accelerator
    • Delaminating strength (EN 1607) 12.9 kPa,
      remaining strength after ageing 7.6 kPa.
  • Formulations 17-20 reaction temperature 130°C. Molratio as formulation 9) DEA:THPA:TMA = 1:0.6:0.3 90 kg DEA was heated to 60°C whereafter 40 kg THPA was added during stirring. The temperature was raised to 95°C whereafter the exothermic reaction continued to raise the temperature to 115°C. A Further 38.5 kg THPA was added and the temperature allowed to rise to 130°C and maintained for 10 minutes before 49.6 kg TMA was added. The temperature was held at 130°C for 60 minutes and then cooled to approximately 50°C by the addition of 120 l of water. The reaction mixture was kept at this temperature for 60 minutes until all TMA was dissolved.
    • Rest monomers: 39% DEA of added, rest monomer 18% of added anhydrides.
    • Average molecular weight of oligomers 600.
    • Before further dilution with water a base is added until a pH of about 6-8, preferably 7 results. The base may be an alkalihydroxide, amine or ammoniumhydroxide.
    • In these formulations ammoniumhydroxide was used. Evaporation loss of binder solids was between 15 and 17%.
  • Before use an accelerator/crosslinker, a silane and water was added to 25% solids content. Product quality when using 3% of solids phosphonic acid as curing accelerator (formulation 17)
    Delaminating strength (EN 1607) 15.2 kPa,
    remaining strength after ageing 9.1 kPa.
    Product quality when using PAA as curing agent (Rohm and Haas Acumer 1510), (formulation 20).
    Delamination strength (EN 1607) 11.2 kPa,
    remaining strength after ageing 4.5 kPa.
  • High silane addition as described in the example above.
  • Silane results
  • The binder mixture in formulation 17 was used for testing different amounts of silane addition.
  • The binding strength was performed according to the grit bar test.
  • Preparation and testing of selected binder samples to evaluate the binding strength towards shots with mineral fibre composition (Grit bar test)
  • Shots with size between 0.25 and 0.5 mm diameter were used to make bars with dimensions 140 mm x 25 mm x 10 mm.
  • For making the bars 90 ml binder solution with 15% solids content and from 0.2%-3.0% silane coupling agent of binder solids were mixed with 450 g shots.
  • The coupling agent was gammaaminopropyltriethoxysilane.
  • To some of the binder solutions were added NaH2PO2-H2O (3% of binder solids) as curing accelerator.
  • Out of the 450 g shots mixed with binder solution can be made 8 bars which is cured 2 hours at 200°C in an incubator.
  • Four of the bars were broken directly (dry strength), the other 4 are placed 3 hours in 80°C water before they are broken (wet strength).
  • The binding strength was determined by breaking the bars in a measuring device, where the clamping length is 100 mm and the velocity of the compressing beam was 10 mm/min. Using the clamping length, width and thickness of the bars, the bending strength was determined in N/mm2.
  • Grit bar test results:
  • Bending strength Dry N/mm2 Wet N/mm2 0.2% silane 9 4 0.4% silane 9 4 0.6% silane 9 5 1.0% silane 9 7 1.2% silane 9 8 3.0% silane 9 8
    A resin made according to formulation 22 with a mole ratio DEA:ADP = 1 : 0.5, reaction temperature 130°C was mixed with 25% Acumer 1510 solids of resin solids and further added
    different amounts of silane VS 142.
  • Grit bar tests show:
  • Bending strength Dry N/mm2 Wet N/mm2 0.2% silane 9 3 0.4% silane 9 3.5 0.6% silane 9 5 1.0% silane 9 7 1.2% silane 9 8 3.0% silane 9 8
    The aged (wet) strength is improved by adding higher amounts of silane. (Silan VS 142 as a % of the sum solids)
  • Conclusions based on results:
  • Water addition at the end yielded less unreacted starting monomers, whereby water addition at the end or together with the second anhydride gives higher yield of amides in the resin. See table 1.
  • SCA as second anhydride yielded short curing time and high yield of amides in the reaction product.
  • When the amount amides in the reaction product is too high(>40% of the DEA added) the delamination strength after ageing of the mineral wool products proved to be poor.
  • The preferable mol.ratio DEA to anhydride proved to be 1:0.9-1.2, whereby higher ratios of anhydrides may provide less water soluble resin.
  • Water should be added at the end, immediately before, or together with the second anhydride.
  • The first anhydride is preferably THPA, mol.ratio 0.5 to 1 related to DEA.
  • The preferred second anhydride is TMA or PTA.
  • SCA as second anhydride yielded good strength before ageing, but poor ageing stability.
  • An example of a preferred resin consists of 30% polymer of DEA, THPA and TMA, 15% DEA monomer, 10% THPA monomer reacted with water to diacid, 5% TMA monomer reacted with water to triacid 40% water.
  • An example of another preferable resin consists of about 40% or more polymer of DEA, THPA and TMA, about 10% or less DEA monomer, about 10% or less THPA monomer and TMA monomer reacted with water to diacid, triacid respectively and about 40% waster.
  • In the polymer about 50% of the DEA which has reacted to a polymer is preferably an amide and the other 50% has preferably reacted to an ester.
  • The invention is not limited to the above description but is determined by the following claims.

Claims (30)

  1. A process for providing a binder for mineral fibers, comprising the steps of:
    mixing together under reactive conditions an anhydride and an amine selected from N-substituted ß-hydroxyalkyl amines, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol and tris(hydroxymethyl)aminomethane, whereby water is added thereto once substantially all the anhydride is dissolved in and/or has reacted with the amine.
  2. A process according to claim 1 wherein a second anhydride is added to the reaction mixture.
  3. A process according to claim 2 wherein the water is added to the reaction mixture when the first anhydride has reacted, immediately before or together with the second anhydride, or when substantially all the second anhydride is dissolved in the mixture of the first anhydride and the amine.
  4. A process according to any one of the preceding claims wherein water is added in an amount to make the reaction mixture easily pumpable at room temperature.
  5. A process according to any one of the preceding claims wherein the amine is heated firstly to a temperature of at least 40°C, preferably at least 50°C and most preferably to about 60°C, whereafter the first anhydride is added, and the reaction temperature raised to at least about 70°C, preferably at least about 95°C, and most preferably to at least about 120°C.
  6. A process according to claim 5 wherein the reaction temperature is raised to at least about 90°C, preferably at least 120°C, and more preferably about 130°C, and is below about 200°C, preferably below about 170°C, and more preferably below about 150°C.
  7. A process according to claims 5 or 6 wherein the second anhydride is added to the reaction mixture when substantially all the first anhydride is dissolved.
  8. A process according to any one of the preceding claims wherein the first anhydride is an aliphatic anhydride.
  9. A process according to any one of the claims 2 - 8 wherein the second anhydride is an aromatic anhydride.
  10. A process according to any one of the preceding claims, wherein the first aliphatic anhydride is selected from tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, succinic anhydride, nadic anhydride, maleic anhydride and glutaric anhydride.
  11. A process according to any one of the preceding claims 2 - 10 wherein the second aromatic anhydride is selected from phthalic anhydride, trimellitic anhydride, pyromellitic di-anhydride and methylphthalic anhydride.
  12. A process according to any one of the preceding claims wherein the N-substituted ß-hydroxyalkyl amine is selected from diethanolamine, 1-methyldiethanolamine, 1-ethyldiethanolamine, n-butyldiethanolamine, 1-methylisopropanolamine and 1-ethylisopropanolamine, and preferably is diethanolamine.
  13. A process according to any one of the preceding claims comprising the further step of addition of one or more of the following additives:
    an accelerator in order to accelerate curing speed, resin additives such as aminosiloxane to improve adhesion to fibre surface, thermal and UV stabilizers, surface active compounds, fillers such as clay, silicates, magnesium sulfate and pigments such as titanium oxide, hydrophobizing agents such as fluorine compounds, oils, preferably mineral and silicone oils, and corrosion inhibitors.
  14. A process according to claim 13, wherein the accelerator is selected from the acid or corresponding salts of phosphorous acid, phosphoric acid, phosphonic acid, phosphinic acid, citric acid, adipic acid and ß-hydroxyalkylamides.
  15. A process according to claim 13 or 14, wherein the additives are selected from mono-, di- and polysaccharides, such as sucrose, glucose syrup, modified starch, starch, urea, dicyandiamide, polyglycols, acrylics, furfural, carboxymethyl cellulose and cellulose, polyvinyl alcohol and melamine.
  16. A process according to any one of the preceding claims, further comprising the addition of a cross-linking agent, wherein the cross-linking agent preferably comprises a carboxylic acid group containing polymer, preferably in the form of polyacrylic acids or polymethacrylic acids.
  17. A process according to claim 16 wherein the polycarboxylic acid cross-linking agents are added to the reaction mixture to be present in the weight percentage range of 5 - 25 and preferably about 20 wt.%.
  18. A process according to any one of the preceding claims, wherein the mole ratio of the amine to the first anhydride lies in the range of 1.0 : 0.1 - 2.0, preferably 1.0 : 0.5 - 1.5, and most preferably 1.0 : 0.5 - 1.0.
  19. A process according to claim 18 wherein the amine is diethanolamine and wherein the first anhydride is tetrahydrophthalic anhydride, being present in the mixture at a molar ratio of 1 to 0.5, respectively.
  20. A process according to claim 19, wherein the second anhydride is trimellitic anhydride or phthalic anhydride, wherein the second anhydride is present in the mixture at a lower mole ratio than the first anhydride, preferably in about half the amount of the first anhydride.
  21. A process according to any one of the preceding claims, wherein a base is subsequently added to the reaction mixture, following the water addition.
  22. A process according to claim 21 wherein the base is selected from NH3, diethanolamine, triethanolamine, alkali hydroxides, optionally mixed with a polyacrylic acid.
  23. A process according to claim 21 or 22 wherein the base in the resin reaction mixture adjusts the pH up to about 8, preferably to lie in a range of about 6 to about 8, and most preferably adjusts the pH to about 7.
  24. A process according to any one of the preceding claims wherein an acid is added, preferably before addition of the anhydride and wherein the acid is selected from: adipic acid, citric acid, trimellitic acid, sebacic acid, azelaic acid and succinic acid, and is preferably adipic acid.
  25. A process according to any of the claims 21 - 24, wherein the weight % of the polyacrylic acid in the mixture lies in the range up to 50%, preferably up to 25%, and most preferably up to 20%.
  26. A process according to any one of the preceding claims further comprising the step of adding a silane, preferably in the range of 0.1% - 5%, more preferably 0.2% - 3% and most preferably about 1% by weight of the resin reaction mixture, by weight of the resin solids, whereby the silane is most preferably prehydrolysed gamma-aminopropyltriethoxysilane.
  27. A binder for mineral fibers, obtainable according to any one of the preceding claims 1 - 26.
  28. A binder for mineral fibers obtainable according to claim 2 wherein the polymeric part of the binder has a molecular weight of maximum 2000 and an average molecular weight lying in the range of 500 - 900.
  29. A binder according to claims 27 or 28, having a curing time at 250°C of at the most about 2 minutes, and preferably lying in the range 15 - 55, for example 20 - 40 seconds.
  30. The use of a binder according to any one of claim 27 - 29 for bonding mineral wool products.
EP01960457.8A 2000-07-04 2001-07-03 Binder for mineral wool products Active EP1296903B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP00202335 2000-07-04
EP00202335A EP1170265A1 (en) 2000-07-04 2000-07-04 Binder for mineral wool products
PCT/EP2001/007628 WO2002006178A1 (en) 2000-07-04 2001-07-03 Binder for mineral wool products
EP01960457.8A EP1296903B1 (en) 2000-07-04 2001-07-03 Binder for mineral wool products

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EP01960457.8A EP1296903B1 (en) 2000-07-04 2001-07-03 Binder for mineral wool products
EP09156922.8A EP2075239B1 (en) 2000-07-04 2001-07-03 Binder for mineral wool products and process of preparing the same
SI200131031T SI1296903T1 (en) 2000-07-04 2001-07-03 Binder for mineral wool products

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EP09156922.8 Division-Into 2009-03-31

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EP1296903B1 true EP1296903B1 (en) 2013-08-21

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CA (1) CA2410672C (en)
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Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1382642A1 (en) * 2002-07-15 2004-01-21 Rockwool International A/S Formaldehyde-free aqueous binder composition for mineral fibers
FR2853903B1 (en) 2003-04-16 2005-05-27 Saint Gobain Isover Gluing composition of mineral fibers comprising a carboxylic polyacid and a polyamine preparation process, and resulting products
US7842382B2 (en) 2004-03-11 2010-11-30 Knauf Insulation Gmbh Binder compositions and associated methods
MX2007004416A (en) 2004-10-13 2007-06-11 Knauf Insulation Gmbh Polyester binding compositions.
EP1669396A1 (en) * 2004-12-10 2006-06-14 Rockwool International A/S Aqueous binder for mineral fibers
AU2006202621A1 (en) * 2005-06-30 2007-01-18 Rohm And Haas Company A curable composition
ES2319566T3 (en) * 2005-07-08 2009-05-08 Rohm And Haas Company curable compositions comprising beta-reactive hydroxyamide from lactones.
US7888445B2 (en) 2005-07-26 2011-02-15 Knauf Insulation Gmbh Fibrous products and methods for producing the same
BRPI0617839A2 (en) * 2005-10-26 2013-01-08 Huntsman Int Llc binder for bonding mineral fibers, reaction mixture for preparing binder, process for preparing reaction mixture, use of binder, process for providing a bound mineral fiber product, and, mineral fiber product
GB0604315D0 (en) * 2006-03-03 2006-04-12 Univ Leeds Composition and method
US9169157B2 (en) 2006-06-16 2015-10-27 Georgia-Pacific Chemicals Llc Formaldehyde free binder
US7795354B2 (en) 2006-06-16 2010-09-14 Georgia-Pacific Chemicals Llc Formaldehyde free binder
US7803879B2 (en) 2006-06-16 2010-09-28 Georgia-Pacific Chemicals Llc Formaldehyde free binder
EP1873188A1 (en) * 2006-06-19 2008-01-02 DSMIP Assets B.V. Polyesteramides and compositions comprising them
EP1889819A1 (en) * 2006-08-18 2008-02-20 Rockwool International A/S Binder for mineral fibres
EP1892225A1 (en) * 2006-08-23 2008-02-27 Rockwool International A/S Aqueous urea-modified binder for mineral fibres
EP1892485A1 (en) * 2006-08-23 2008-02-27 Rockwool International A/S Solar collector
EP1897433A1 (en) * 2006-09-06 2008-03-12 Rockwool International A/S Aqueous binder composition for mineral fibres
EP2109594A1 (en) * 2007-01-25 2009-10-21 Knauf Insulation Limited Mineral fibre insulation
EP2108026A1 (en) 2007-01-25 2009-10-14 Knauf Insulation Limited Composite wood board
US9828287B2 (en) 2007-01-25 2017-11-28 Knauf Insulation, Inc. Binders and materials made therewith
WO2008127936A2 (en) 2007-04-13 2008-10-23 Knauf Insulation Gmbh Composite maillard-resole binders
GB0715100D0 (en) 2007-08-03 2007-09-12 Knauf Insulation Ltd Binders
EP2085365A1 (en) 2008-02-01 2009-08-05 Rockwool International A/S Method of producing a bonded mineral fibre product
EP2093266A1 (en) 2008-02-25 2009-08-26 Rockwool International A/S Aqueous binder composition
EP2230222A1 (en) 2009-03-19 2010-09-22 Rockwool International A/S Aqueous binder composition for mineral fibres
CA2770396A1 (en) 2009-08-07 2011-02-10 Knauf Insulation Molasses binder
BR112012028526A2 (en) 2010-05-07 2016-07-26 Knauf Insulation Method of preparing a collection of bonded material with a polymeric, heat-cured, cured binder and composition
JP6223823B2 (en) 2010-05-07 2017-11-01 ナフ インサレーション エセペーアールエル Carbohydrate polyamine binder and material made using the same
BR112013001630A2 (en) * 2010-07-23 2016-05-24 Rockwool Internat product of bonded mineral fibers having high resistance to fire and exothermic decomposition at elevated temperatures.
EP2415721A1 (en) 2010-07-30 2012-02-08 Rockwool International A/S Compacted body for use as mineral charge in the production of mineral wool
FR2964012B1 (en) 2010-08-31 2017-07-21 Rockwool Int Growing plants in a substrate base mineral wool comprising a binder
WO2012037451A2 (en) 2010-09-17 2012-03-22 Knauf Insulation Gmbh Organic acid carbohydrate binders and materials made therewith
EP2637982A1 (en) 2010-11-09 2013-09-18 Rockwool International A/S Mineral fibre product having reduced thermal conductivity
EA027765B1 (en) 2011-05-17 2017-08-31 Роквул Интернэшнл А/С Growth substrate products and their use
EP2549006A1 (en) * 2011-07-22 2013-01-23 Rockwool International A/S Urea-modified binder for mineral fibres
US20140350142A1 (en) 2011-12-02 2014-11-27 Rockwool International A/S Aqueous binder composition
GB201206193D0 (en) 2012-04-05 2012-05-23 Knauf Insulation Ltd Binders and associated products
GB201214734D0 (en) 2012-08-17 2012-10-03 Knauf Insulation Ltd Wood board and process for its production
CH709783A1 (en) 2014-06-16 2015-12-31 Flumroc Ag A process for producing a water-soluble prepolymer, and the prepolymer, prepared by the method.
EP2990494B1 (en) 2014-08-25 2017-01-11 Rockwool International A/S Biobinder
EP3037393A1 (en) 2014-12-23 2016-06-29 Rockwool International A/S Improved Biobinder
EP3135649A1 (en) 2015-08-28 2017-03-01 Rockwool International A/S Mineral wool product
EP3135648A1 (en) 2015-08-28 2017-03-01 Rockwool International A/S Mineral wool product
EP3184496A1 (en) 2015-12-23 2017-06-28 Rockwool International A/S Peg-binder
EP3184497A1 (en) 2015-12-23 2017-06-28 Rockwool International A/S Binder comprising a cyclic oxocarbon
WO2018206132A1 (en) 2017-05-11 2018-11-15 Rockwool International A/S Mineral wool binder
CN109153194A (en) 2016-05-13 2019-01-04 洛科威国际有限公司 A method of production includes the mineral wool product and such product of multiple thin slices

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341573A (en) * 1963-06-05 1967-09-12 Hollingshead Corp Polyamide esters for hydraulic fluids and method of making the same
US4074988A (en) * 1975-12-03 1978-02-21 Ppg Industries, Inc. Glass fiber coating method
US4978738A (en) * 1988-07-12 1990-12-18 Hoechst Celanese Corp. High molecular weight, thermally soluble polyimides
CA2212470A1 (en) * 1996-08-21 1998-02-21 Rohm And Haas Company A formaldehyde-free, accelerated cure aqueous composition for bonding glass fiber-heat resistant nonwovens
NL1007186C2 (en) * 1997-10-01 1999-04-07 Dsm Nv beta-hydroxyalkylamide group-containing condensation polymer.
NL1008041C2 (en) * 1998-01-16 1999-07-19 Tidis B V I O Use of a water-soluble binder system for the production of glass fiber or rock wool.
EP1086932A1 (en) * 1999-07-16 2001-03-28 Rockwool International A/S Resin for a mineral wool binder comprising the reaction product of an amine with a first and second anhydride

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AU2001281948B2 (en) 2006-12-21
CA2410672C (en) 2010-03-09
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US20040024170A1 (en) 2004-02-05
HU0301295A2 (en) 2003-08-28
CA2410672A1 (en) 2002-01-24
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WO2002006178A1 (en) 2002-01-24
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EP2075239B1 (en) 2017-05-17
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AU8194801A (en) 2002-01-30
HU0301295A3 (en) 2011-10-28
DK1296903T3 (en) 2013-10-21
EP1296903A1 (en) 2003-04-02
EP2075239A3 (en) 2010-04-07
SI1296903T1 (en) 2014-02-28

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